Cement compositions containing glass fibres

ABSTRACT

FIBRE REINFORCED CEMENTITIOUS PRODUCTS ARE DESCRIBED COMPRISING GLASS FIBROUS MATERIAL DISTRIBUTED THROUGHOUT A CEMENT MATRIX, IN WHICH THE GLASS IS ONE HAVING PER SO A DEGREE OF ALKALI RESISTANCE WUCH THAT WHEN TESTED IN THE FORM OF AN ABRADED FIBRE OF LENGTH 2 1/2 INCHES AND DIAMETER OF FROM 0.4 TO 1.0X10-3 INCHES SAID FIBRE HAS A TENSILE STRENGTH OF AT LEAST 100,000 P.S.I. AFTER TREATMENT WITH SATURATED AQUEOUS CA(OH)2 SOLUTION AT 100*C. FOR 4 HOURS FOLLOWED BY SUCCESSIVE WASHINGS AT AMBIENT TEMPERATURE WITH WATER, THEM WITH AQUEOUS HYDROCHLORIC ACID (1%) FOR 1 MINUTE, WATER, ACETONE, FOLLOWING BY DRY ING. SAID FIBRE EXPERIENCING NOT MORE THAN 10% REDUCTION IN DIAMETER DURING SAID TEST. THE REINFORCEMENT OF PORTLAND CEMENT STRUCTURES BY FIBRES OF DIAMETER 0.4 TO 1.0 X 10-3 AND LENGTHS OF UP TO 4 INCHES IS DESCRIBED. ALKALI RESISTANT GLASSES USEFUL FOR PRODUCTION OF THESE PRODUCTS COMPRISES THE CAO-MGO-AL2O3-SIO2 GLASSES IN CLUDING THOSE IN THE ANORTHITE FIELD, SILICA ZIRCONIA GLASSES AND SILICA STANNIC OXIDE GLASSES. THE PRODUCTS HAVE OUTSTANDING DURABILITY AND IMPACT RESISTANCE.

. p I L Uruted States Paten 3,783,092 CEMENT COMPOSITIONS CONTAINING GLASS FIBRES Amalendu Jyoti Majumdar, Watford, England, asslgnor to National Research Development Corporation, .London, England No Drawing. Continuation-impart of applications Ser. No. 649,463, June 28, 1967, Ser. No. 748,645, July 30, 1968, and Ser. No. 31,184, Mar. 26, 1970, all now abandoned. This application Mar. 23, 1971, Ser. No. 127,361

10 Claims priority, application Great Britain, Apr. 3, 1969,

Int. Cl. B32b 5/02; C04b 31/06 U.S. Cl. 161--170 17 Claims ABSTRACT OF THE DISCLOSURE Fibre reinforced cementitious products are described comprising glass fibrous material distributed throughout a cement matrix, in WhlC t e g ass is one having per se a degree of alkali resistance such that when tested in 20 the form of an a ra e re of length 2% inches and diameter of from 0.4 to 1.0 10- inches said fibre has a tensile strength of at least 100,000 p.s.i. after treatment with saturated aqueous Ca(OH) solution at 100 C. for 4 hours followed by successive washings at ambient temperature with water, then with aqueous hydrochloric acid (1%) for 1 minute, water, acetone, following bydrying, said fibre experiencing not more than 10% reduction in diameter during said test.

The reinforcement of portland cement structures by fibres of diameter 0.4 to 1.0 10- and lengths of up to 4 inches is described.

Alkali resistant glasses useful for production of these products comprise the CaO-MgO-Al O -SiO glasses including those in the anorthite field, silica zirconia glasses, and silica stannic oxide glasses.

The products have outstanding durability and impact resistance.

40' This application is a continuation-in-part of application Ser. No. 649,463, filed June 28, 1967, and of application Ser. No. 748,645, filed July 30, 1968, and of application Ser. No. 31,184, filed Mar. 26, 1970, all now abandoned.

on a large scale, asbestos-cement products are not entirely suitable for many applications but no acceptable 5 substitute for asbestos has yet been found. Such cementasbestos products are described by Kozacik in U.S. Pat. No. 3,354,031, wherein asbestos serves as a reinforcement and a very small amount of mineral glass fibre is included to serve as a filtration aid in producing the products.' With the development of glass fibre materials, proposals have been made to substitute glass fibres for asbestos in typical structural and other components but these proposals have in general failed to lead to products of acceptable strength and durability. One approach to increase the strength of cementitious products with glass fibres is described in U.S. Pat. 2,793,130. The glass fibres are provided, before incorporation in a cement slurry, with a water-insoluble coatin The coating, designed to impmwndifg'bf'gfl'fibe and cementitious 7 materials, is formed by reaction WW -salt 3114 {1/311151 soluble oxide or hydroxi e. owever,

Patented Jan l, 1974 the principal reason for the lack of success of previous proposals is that the strongly alkaline environment, especially in products based on portland cement, is sufliciently severe in certain cases to disintegrate glass fibres and for this reason it has been assumed that such fibres cannot be applied successfully as reinforcing materials without resort to protective measures which add considerably to the cost of production of the composite materials. It is found, for example, that protective coatings are insufiiciently reliable because in practice it is almost imposisble to avoid discontinuities in the coating with the result that the underlying fibre is exposed to a considerable extent to the corrosive action of the cement.

Among the properties of certain glass compositions, a degree of resistance to alkaline solutions has been observed in tests carried out with bulk specimens of glass. These observations, however, have not been recognized as having any bearing on the problem of producing satisfactory cement/glass composite structures in which the glass, being in fibre form, is thereby exposed to the corrosive environment over a considerably large surface area per unit weight.

It has now been found that glass fibre reinforced cement products having outstanding properties can in fact be obtained provided that the glass in fibre form has sufiicient alkali resistance to meet the requirements of a test which will be specified hereinafter. It is noted that alkali resistance of the glass fibres is essential for the glass reinforced cementitious products of this invention. This is to be contrasted with prior descriptions of glass fibres exhibiting corrosion resistance to atmospheric conditions, which are generally acidic. One such description is given in U.S. Pat. No. 3,095,311 wherein glasses are shown to resist the action of hydrochloric acid.

In my co-pending applications Ser. Nos. 649,463 and 748,645, I have described composite fibre/cementitious products in which the fibrous reinforcing material is primarily a glass having per se a degree of alkali resistance 'such that when tested in the form of an abraded fibre washing at ambient temperature with water, then with aqueous hydrochloric acid (1%) for 1 minute, water, acetone, followed by drying, said fibre experiencing not more than 10% reduction in diameter during said test. Preferably the tensile strength of such fibres after the specified treatment is at least 200,000 p.s.i.

In the case of products based on portland cement excellent reinforcement is provided by means of fibres having a ,diameter of about 0.4 to about 1.0 10- inches. In practice it is particularly convenient to employ short fibres of length up to about 4 inches, for example, fibres having a length of the order of 2.5 inches.

Glass fibre-reinforced concrete and other cementitious materials produced in accordance with this invention have been found to exhibit such high strengths that for certain applications the glass fibres may be used in either partial or complete replacement of steel in structural components.

It will be appreciated that suitable glass compositions for use in accordance with this invention may be determined by forming fibres therefrom and subjecting such fibres to the test described above.

For reinforcing cementitious matrices at temperatures higher than ambient, it is desirable, moreover, that the fibres exhibit resistance to attack by alkali metal hydroxides, in addition to attack by Ca(OH) A test for this resistance, similar to the previously mentioned test for attack by Ca(0H)- is as follows:

{ An individual glass fibre having a diameter in the range of from 0.4-10x10 inches and a len'gth'of 2% inches is exposed to attack by NNaOH solution for 1% hours at 100 C. After exposure, the fibre is taken out of the solution at room temperature, washed three times with distilled water, then with dilute HCl (1%) for V2 minute, followed by several washes with distilled water. Finally, the fibre is washed with acetone twice and dried, after which its tensile strength is determined by measuring the breaking load with an Instron testing machine and estimating the fibre diameter by an optical microscope.

A glass fibre exhibiting a tensile strength of at least 100,000 and preferably at least 200,000 lbs/sq. in. after the test, and experiencing during the test a reduction in diameter no greater than has the required properties for reinforcing the cementitious matrices at higher than ambient temperatures.

In assessing the suitability of glass fibres for reinforcing cementitious matrices, it is also instructive to study the behavior of the fibres in a cement efliuent solution at different temperatures and difierent ages. The exact composition of the solution phase produced when portland cement is mixed with water varies greatly with cements from different sources. A synthetic analogue of such a solution can, however, be prepared in the laboratory which will have ionic concentrations of Na+- and K+ similar to those found in the solution phase of average portland cements. If this solution is then made saturated with respect to Ca(OH),, it represents approximately the compositions of the solution phase of a portland cement slurry regarding the concentrations of hydroxides. A typical cement etfluent composition is:

The desired alkali resistance properties are exhibited by fibres of certain glasses of Ca0-Al O -MgO-SiO type, wherein the oxide ratios are selected so that the composition of the glass lies within the anorthite primary phase volume of the CaO-Al O -SiO -MgO phase diagram or in its immediate vicinity, and the glasses are substantially boron free i.e. have virtually no B 0 I Such phase diagram is described in the article Quaternary Slags CaO-MgO-AI O -SiO Initial Crystallization and Fields of Crystallization at Constant Magnesia Planes" by G. Cavalier and M. Sandrea-Deudon, Revue de Metallurgie, 57, 1143-1157 (December 1960).

Within this group of glasses one preferred class of glasses is represented by those in which the main oxide percentages are selected to be in the following ranges:

Oxide- Weight percent sio, 50-05 A1208 12-21 CaO 10-21 MgO 3-10 glasses in the CaO-Al O -SiO -MgO phase diagram, it may be assumed that optional substituent ZrO; substitutes for SiO,; optional substituents Tio Fe 0 Cr O for A1 0 and optional substituents BaO, MnO, Z110 for CaO.

The optional substituents, if their percentages are high, may sometimes change the composition of the glass in such a way that it falls outside the anorthite primary phase volume of the Ca0-Al Q -Mg0-SiO system but still exhibit adequate alkali-resistance. An example of such a glass is one containing a relatively high total percentage of MgO+MnO, say up to 20%.

The present invention comprises a composite fibre/ cementitious product in which the fibrous reinforcing material is at least partly and preferably primarily or wholly glass fibrous material, the glass having sufiicient alkali resistance per se to pass the test hereinbefore specified, said fibrous material being distributed throughout a cement matrix.

The present invention also provides a process for producing a reinforced cementitious product comprising incorporating into the raw cementitious mix prior to setting glass fibrous material, the glass having alkali-resistance sufiicient to pass the abovementioned test.

It will be appreciated that the glass fibre tested should be initially in an abraded state as opposed to the virgin" state in which it is originally made at the point of actual manufacture by pulling, extrusion or the like. The virgin condition of a glass fibre is rapidly degraded to the stable abraded condition by manual or mechanical handling, with simultaneous substantial decrease in strength. This is because the initial strength of the fibre, in the low diameter range contemplated, is determined prior to alkali attack primarily by the surface condition of the fibre. In the case of glass fibres of diameter in the range 0.5-1.0X 10- inches and of oxide composition 19% CaO, 21% A1 0 55% SiO 5% MgO, a "virgin strength when freshly drawn of around 400,000-500,000 lbs./ sq. in. corresponds to an abraded strength around 200,000 lbs/sq. in.

The glasses used for the purposes of this invention are preferably those capable of fiberization under conditions which are acceptable and convenient on the scale of commercial manufacture. Common methods of fiberization are continuous pulling (or spinning), blowing and centrifugation. The viscosity-temperature relationships of the glasses in the anorthite field are such as to enable fibres to be conveniently made by pulling in particular. Pulling of fibres is in general much facilitated by including in the glass composition in any event a minor amount of a fluxing agent. The fluxing agent can both reduce the melting point of the glass and the viscosity of the melt, so providing a considerable advantage in the commercial manufacture of the fibres. A preferred fluxing agent is CaF, but other fluxing agents already known for other glasses can be employed, for example P 0 alkali metal oxides and MnO. Mixtures of fluxing agents may also be employed. It is noteworthy that MnO is effective as a fluxing agent as well as being a desirable optional substituent for the provision in the glass of the desired alkaliresisting properties. The quantities of fluxing agent or agents to be included in the glass depends on the composition of the glass to be drawn into fibres-its refractoriness and its viscosity-temperature relationship. It may be up to 10% by weight of the overall oxide mix of the glass, although usually less. For CaF- in some of the glasses studied, a suitable quantity is 3% by weight of the total mix, but significant improvement in pulling characteristics can still be achieved with the incorporation of much smaller percentages.

As compared with products comprising fibres of the glasses mentioned by specific composition above, products of improved properties are obtained'if use is made of fibres derived from certain siliceous glasses containing relatively high proportions of ZrO, as described in US. application Ser. No. 748,645. The glasses may also contain minor proportions of other oxides, e.g. A1 0 capable of substituting for SiO in the network, but SiO is the dominant glass-forming ingredient. Thus the glass preferably contains as essential ingredient at least 65% SiO and at least 10% ZrO and generally 65%-80% SiO 10-20% Z103. The percentage of ZrO, is preferably about 15% to about 16%. In order to ease glass melting and subsequent fiberization it is desirable to add other oxides, network modifiers, in suitable quantities. Alkali and alkaline earth metal oxides and ZnO are amongst the oxides which can be used to modify the glass structure in this way. Up to 20% Na o has been found adequate t g h although the preferred proportion is somewhat lower, say m modifiers -12%. Generally, the network modifier or will be present in the range of 10-20%. V

Small quantities of other auxiliary oxides whose precise role in the silica-zirconia glass structure is not :known can nevertheless affect its properties in a favorable way" for the production of fibres. Less than 3% of La O has been found adequate to reduce the viscosity of the present glasses without increasing their tendency to crystallization. The network modifiers, and auxiliary-oxides, may also act-as fluxing agents; Li O for .example, acts both .as a network modifier and-fluxing agent. Fluxing agents which are not-also network modifiers will normally be present, however, in a maximum of 10%.

A glass containing about 16% ZrO,, 11% Na O, 1% Li O, 1% A1 0 remainder*(71%) SiO, is capable of being .fiberized at 1450-1500 C. to provide alkaliresistant glass fibres suitable for the purposes mentioned herein. It is most surprising that these glasses are capable of being fiberized on a commercially practicable scale bearing in mind the natures of ZrO, and SiO,. In addition to the limitation imposed by the 1774' C. melting point of platinum, the metal normally used for bushings when making the glass fibres'by spinning techniques, the melt requires to have a suitable viscosity and crystallization has to be avoided. These three factors of melt temperature, viscosity and crystallization are to some extent conflicting. A lower viscosity, whilst assisting drawing, increases the risk-of crystallization since diffusion of the seed nuclei is accelerated, Zr0 is recognized as increasing the refractoriness of the glass, on account of the high melting point of the oxide, andSiO as providing a component in the melt of high viscosity. While SiO ZrQ represent the essential oxides of the glasses for the present fibres, other oxides will therefore usually be added as discussed above. It has also been found that improved fibres and fibre/ cement composites can be derived from certain siliceous glasses containing substantial proportions of SnO,. Also in' accordance with this invention improved glasses, glass fibres, and composite fibre/cementitious products in which the glass fibres are distributed throughout a cement matrix, 'are"those in which the glass comprises SiO as the dominant glass forming ingredient, an alkali metal oxide oralkaline earth metal oxide or ZnO as the network modifier, and more than 5% by weight of Sno Preferstrength and durability, the glass contains at least 8%. S1103.

In practice convenient tin oxide glass compositions are those containing at least 55% SiO, and a network modifier which is preferably Na O, but may alternatively be:

.45 ably for the production of composites of outstanding Analysis of the raw mix In order to ease melting and subsequent fiberization fluxing oxides may also be included, in amounts in the range of 1-10% of the total weight of the other components of the oxide mix. U 0 and La O are examples of 5 two such oxides, being used preferably in amounts in the range of l-3%.

The glass fibres contemplated herein have such a high degree of resistance to alkali, as defined above, that the surfaces thereof need not be coated with a water-insoluble coating of the type proposed by Shannon in US. Pat. No. 2,793,130 to keep the surfaces from contact with the cementitious materials. lfnrthermore, it is c on templated that 'onal materials siiesmssaror'sinfigbr coating ng i ssiimes can be used ene are emp oye as an aid inmdhhg of glass fibres. When contacted with a water/cement slurry and as the desired reinforced cementitious products are formed, a substantial portion of the size is often unavoidably removed from the glass fibres, thus bringing fibre surfaces into direct contact with the corrosive environment of the slurry. Conventional sizes which can be employed are for example those based K on 1 in etate contain 'f desired, a silane aditrve and a wetting a eat.

Desrra'bly, alkali-resistant glass fibres constitute the sole or at least a major component of the total fibrous reinforcement material in composites according to this invention. However, the use of other fibrous materials providing reinforcement supplementary to that of the glass fibres is not excluded, especially fibres of an artificial nature such as, for example, carbon fibres sually the supple mentary fibres will presen in lesser amount th the glass fibres although the use of comparable quantiti s, and sometimes equivalent amounts weight for weight, may be recommended for certain kinds of composite 3 products. Chopped or other fibrous forms of glass may be used e.g. g 1a s s wool.

Exampl iable glass fibres and therefrom will now be described.

EXAMPLE 1 products made Glasses of composition as set out in the accompanying Table 1 were pulled into single filaments with diameters in range 0.4-1.0X 10- Inc lnitial abraded strengths in the region of from 150,000-400,000 lbs./ sq. in. They were then tested for alkali-resistance according to the method previously described, with the results given in the table.

The table also provides by way of comparison corresponding results obtained for a filament of a standard low alkali borosilieate glass known in the trade under the name E-glass, and containing 8% B 0 The results of this table indicate that the glass fibres are particularly suitable for reinforcing portland cement structures, and are substantially superior in this respect to fibres of E-glass.

EXAMPLE 2 Glass similar to those in Table 1 but containing a much higher proportion of MnO is also suitable as reinforcing fibres. The performance of a glass fibre made from typical compositions of this family is shown in Table 2.

TABLE 1 Alkali-resistance Tensile strength redugti h iii Aft t t B r te 0 er es number CaO 8101 A; MgO T10: MnO CnF: diameter (lbs./sq. in.) (lbs/ c 21 in? 55 21 N11 000 15 5a 21 4 1201000 20 I% 55 17. 7. 5 180, 000 255, 000 6O 15 N11 190, 000 170, 000 s 55 -10 Nil 250,000 430,000 E 9 70, 000 250, 000

TABLE2 Analysis of the glass Alkali-resistance Percent Tensile strength redue- Glass tion in After test Before test number 000 Hi: A120: MgO MnO diameter (1bs./sq.in.) (1bS./sq. in.)

In a preferred way of making fibre-reinforced cementbased composites, a high water/solid ratio is used initially for uniform dispersion of fibres and the excess water is removed by suction followed by pressing. Complicated shapes can be made by spray mixing of cement slurry and glass fibre on the surface of perforated moulds connected to a vacuum pump.

Composites measuring 4" x 1" x A" have been made by this method using.single-filament uncoated fibres derived from some of the g asses re erre to e a ve examples and portland cement. The proportion of glass fibre in the composites was 0.5 gm. of glass to approximately 30 gms. of cement. The initial water/cement ratio in the slurry was 0.8, which fell to 0.3 after suction. Glass fibres measuring 4" in length were placed by hand in the tension zone of these composites during casting. A perforated mould was used and the excess water removed by suction. After demoulding, the composite test specimens were stored in a constant temperature (64 F.), constant humidity (90% R.H.) room. Different curing conditions were used and the flexural strength of the test specimens were determined at different ages. Results are given in Table 3 for a typical alkali-resistant glass, the glass No. 1 in Table l, in comparison with the previously mentioned E-glass. The values given are for flexural strengths in terms of lbs/sq. in.

In further comparison, asbestos-cement boards of thickness and containing -15% asbestos gave an ultimate flexural strength of 4000 lbs/sq. in.

It should be noted that no atempt was made to optimize the fibre content of composites in Table 3 toyield the highest possible fiexural strength; also, the strengths given in Table 3 are average values only and do not refiect the wide scatter observed in the tests.

Results are given in Table 5 for the resistance exhibited at C. by filaments of glass 1 and E-glass using as alkali in the test previously described withan alkali metal hydroxide, a cement efliuent solution of the com as listed in this table are higher than those in Table 4. This is due to the fact that the fibres were tested in this case soon after they were pulled and did not have the chance to reach their abraded" strength, which is always substantially lower than the virgin strength as previously described.

The diameter of the fibre glass No. I remained unchanged after the tests. E-glass fibres were so badly attacked in the test that their diameters could not be measured very accurately afterwards. However, in each case they were found to be definitely smaller than those of the fibres before the test.

In calculating tensile strength of E-glass fibres at all ages after the test, it has been assumed that the diameter remained the same as before the test.

Table 6 provides comparable alkali-resistance test results in the instance when the alkali employed is NNaOH as described above. a

TABLE 3 After 7 After 28 After After 7 days After 7 days days in days in days in in water and in water and Glass number water water water 21 days in air 83 days in air E-glsss 4, 470 4, 350 a, 930 4, 050 a, 000

In composites made with single filament glass fibre it ,TABLEs is ditlicult to avoid uneven dispersion of the fibres 1n the 55. man 818mm, mix; hence the wide variation m results. eg fi Tensile strength X A l on E MPLE 3 Glass number in diameter After test Before test A glass of composition as set out in the accompanying 5 185.000 210,000 60 59 200,000 255,000

Table 4 glass No. 1 was pulled into sin le filaments with a diameter in the range 0.41.0 10- inches. 71 filament was tested for alkali-resistance according to the method previously described when using Ca(OH) as alkali, in comparison with a similar filament of a standard low It will be noted that the apparent increase in strength due to NaOH attack in the case of E-glass is due to the alkali borosilicate glass known under the name E-glass, 65 y large reduction of the diamemr 0f the fi esf the with the results given in the table.

attack progresses as vigorously as is indicated by this test, there would shortly be no glass fibre left at all to reinforce the cementitious matrix.

The result of Tables 4, and 6 indicate that fibres of the glass are particularly advantageous for reinforcing portland cement structures. Further tests have shown that at this temperature (80' C.) fibres products from glass No. 1 when kept immersed in the cement efiiuen solution for a period of two weeks still retain some measurable tensile strength. After 96 hours exposure, the E-glass fibres could not be tested.

Results are given in Tables .7 and 8 for the flexural strengths of portland cement composites reinforced by fibres of glass No. 1 (two sets of results) in comparison with strengths for composites reinforced by fibres of E-glass. The values given are for fiexural strengths in terms of lbs/sq. in. Manufacture of the composites and the test conditions were carried out as described in my earlier patent application No. 649,463.

10 in the range 0.4-0.5X 10- inches, and filamentof each glass was tested for alkali-resistance according to the method previously described using Ca(OH) as alkali. The results are given in Table 11.

Results are given in Table 12 for the resistance exhibited at 80 C. by filaments in the test previously described using, instead of an alkali metal hydroxide, the typical cement eflluent solution of composition given hereinbefore.

Table 13 provides comparable alkali-resistance test resl-flggilg r igg when the alkali employed is NNaOH as descri e above. The filaments again had diameters in the range of 0.4-0.5X 10 inches.

In these tables, the quoted tensile strength values were 15 obtained using apparatus described in Current Paper No.

26/68 (March 1968) issued by the Building Research Station, Bucknalls Lane, Garston, Watford, Hertfordshire, under the title Apparatus for Testing Tensile Strengths of In further comparison, asbestos-cement board of thickness and containing 10-15% asbestos gave an ultimate fiexural strength of 4000 lbs/sq. in.

Flexural strengths of composites fabricated in a similar fashion but cured at 50 C. under water are given in Table 8 for composites made with glass No. 1 and E-glass fibers and ordinary portland cement (two sets of results in each case).

TABLE 8 28 days 90 days 7 days in water in water Glass number in water at 50 C. at 50 C.

Long term results on flexural strengths, again in terms of lbs./sq. in. of composites made with glass No. 1 fibres are set out in Table 9.

TABLE 9 In water In air after first 7 days in water 180 365 days. 180 days 365 days. 5,370 p.s.i 4,360 p.s.i. 5,400 p. 4,680 p.s.i. (Average of 6) (Average of 3). (Average of 6)..- (Average of 3).

These values refer to the second series of values given for glass No. 1 in Table 7. The values given in Table 7 are averages of nine results and cannot be compared, in the strictest sense, with the present results. Although a drop in strength is noted after one year, these results are vastly superior to those obtainable with E-glass fibres.

It should be noted that no attempt was made to.

Glasses of composition given in Table 10 were used. The amount of fluxing agent is expresed as a percentage of the total SiO Na O, SnO, combined weight. The

glasses were pulled intowith a diameter I gs.

Corroded Glass Fibres (R. S. Gillett and A. J. Majumdar). Composites measuring 4" x 1" it Ms" have been made using single-filament ppcoated fibres derived from the tin oxide glasses of Table -lti by'tire same method as described in Example 2.

Results are given in Table 14 .for the flexural strengths of portland...cement composites reinforced by fibres of glass No. 1. The values given for flexural strengths in terms of lbs/sq. in. Manufacture of the composites and the test conditions were carried out as described in my applications No. 649,463 and 748,645.

TABLE 10.GLASS FIBRE COMPOSITION Analysis of glass (wt. Flux (wt. Tensile percent) percent glass) pristine strength Glass number 810; N810 B: L110 L830: (lbs./in.

TABLE 11.Ca(OH)1 TEST Tensile strength Reduction after test in diameter Glass number (lbs/in!) (percent) TABLE 12.-CEMENT EFFLUENT TEST Reduction- Tensile strength afterin diameter after 2 weeks Glass number 1 wk. 2 wks. 4 wks. 24 Wks. (percent) TABLE 13.NaOH TEST EXAMPLE 5 Tests were carrie dout on cement/ fiber composites comparing the silica zirconia fibres having the composition of glass No. 1 recited in Table 4 above with fibres of E- glass. In this example the cement used was Cement Fondu, a calcium alumin-ate cement manufactured by Lafarge UK. Ltd. The silica-zirconia fiber was supplied in the form of continuous roving consisting of 36-40%. Each strand consiste range 13-15 pm. The E-glass r used in this study was supplied as continuous rovings, each roving comprising strands each having 136 filaments 11-13 pm. in diameter. Both types of glass fibers had a polyvinyl coating on them.

In this method, cement slurry having a high water/dry cement ratio (40-50%) and mmwg chopped in situ to the desired lengths were spraye simu taneously onto a paper-covered, perforated metal face of a suction mould. Spraying was continued until a thickness of 10 to 13 mm. was attained. The top surface was then levelled OE and the excess water extracted by the application-of suction. The quantity of glass No. 1 fibres used was 5% by weight of the wet board at this stage whereas with E- glass 6% by weight was used. Immediately after this the composite boards were removed from the mould, cut into 150 mm. x 1 m. strips with a knife, covered with poly thene sheets and stored under laboratory conditions for 7 days. Whenthe boards had hardened sufficiently, they were sawn into small 150 mm. x 50 mm. specimens and after 7 days storage in the moist environment, the specimens were randomly selected and were placed under different curing conditions. Inthe case of the board made with the alkali resistant fibre, a portion of the board measuring 1 m. x 1 m. was left uncut and this was removed to a 90 percent humidity room for storage subsequent to the initial 7-day moist curing.

In general, three conditions of storage were used: (a) under water at 18 C., (b) in air of 40% RH at 18 C. and (c) natural weatherings. Specimens subjected to natural weatherings were kept in a horizontal position well above the ground on a wooden frame placed on the exposure site.

For each type of GRC composite material stored under the environmental conditions mentioned above, tests were carried out to determine the flexural strength, the tensile strength and the resistance to impact. The flexural and tensile strengths were determined using an Instron testing machine whereas for measuring the impact strength of the material an Izod-type instrument having a capacity of 12 joules was employed. The results are shown in Table 15.

4 filaments having diameters in the in theform of an abraded fibre of length 2 inches and diameter of from 0.4 to 1.0X- inches said fibre has a tensile strength of at least 100,000 p.s.i. after treatment with saturated aqueous Ca(0I-I) solution at 100 C. for four hours followed by successive washings at ambient 15 temperature with water, then with aqueous hydrochloric acid (1%) for one minute, water, acetone, followed by drying, said fibre experiencing not more than 10% reduction in diameter during said test,and being derived from' a glass containing as essential ingredients at least 65% ,7y weight of SiO, and at least 10% by weight of ZrO o 2. A cementitious product according to claim 1, wherein the glass contains 65-80% SiO,, 10-20% ZrO and 10-20% alkali metal oxide.

3. A cementitious product according to claim 1, wherein the glass contains 0 10% of a fluxing agent.

4. A cementitious product according to claim 1, wherein the glass contains up to 20% in total of N330 and U 0.

39 5. A cementitious product according to claim 1', where- 7. A cementitious ,ct. according to claim 1, in

which the cement i portland cement/ 8. A composite fi re cementitious' product comprising fibrous material distributed throughout a cement matrix and subject, where the surface is exposed to the cement matrix, to the corrosive action of said matrix, in which the reinforcing material is primarily a glass having per se a degree of alkali-resistance such that when tested in the form of an abraded fibre of length 2 inches and diameter of from 0.4 to 1.0 l0 inches said fibre has a' tensile strength of at least 100,000 p.s.i. after treatment with saturated aqueous Ca(OH) solution at C. for four hours followed by successive washings at ambient temperature with water, then with aqueous hydrochloric, acid (1%) for one minute, water, acetone, followed by ing ingredient, an alkali metal oxide or an alkaline earth metal oxide or ZnO as a network modifier, and more than 5 by weight of SnO 9. A composite product according to claim 8, in which the glass contains at least 8% Smo TABLE 15 Tensile stre th fl lexural strength Impact strength 1 (p.s.l.) (p.s.i.) (inch-lb./sq.1n.)

Composite 28 days 1 year 28 days 1 year as days 1 year Storage conditions (a) E-glass 2, 050 1,100 6,630 2,730 165 18 Glass No.1- 2,030 2,140 0,000 5,300 145 130 Storage conditions (in E-glass 10,030 5,700 Glass No.1 2,430 2,200 6,660 0,000 m I Water-cured.

Iclaim: V

1. A composite fibre/cementitious product comprising 70 fibrous material distributed throughout a cement matrix and subject, where the surface is exposed to the cement matrix, to the corrosive action of said matrix, in which the reinforcing material is primarily a glass having per se a degree of alkali-resistance such that when tested 75 8-1 8%Sn0;.

13. A composite product according to claim 12, in which the glass contains 70-80% S102, 10-l4% Na o and 10-16% SnO 14. A composite product according to claim 8, in which the glass contains one or more additional oxides as a flux or partial replacement of the glass forming ingredient or network modifier, the total amount of additional oxide or oxides being not greater than 10%.

15. A composite product according to claim 14, in which the amount of additional oxide or oxides is not greater than 5%.

16. A composite product according to claim 14, containing LiO or La O as a flux in the proportion of from 1 to 3%.

which the cement is portland cement.

14 References Cited UNITED STATES PATENTS ALFRED L. LEAVITT, Primary Examiner 10 R. A. DAWSON, Assistant Examiner us. 01. X.R. 106-50, 52, 99; 161-93, Dig. 4

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,783 I Dated January I, 1974 Inventor s) AMALENDU JYOTI MAJUMDAR It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 1, line 11 Replace "application...l7,448/69" by the following;

--applications Great'Britain, July 11, 1966, 31025/66; Feb 2,- 1967, 5070/67; Aug. 4, I967,

3590 l/6 7; and Apr. 3, I969, l7448/69--.

Signed and sealed this 17th day of September 1974.

(SEAL) Attest: V

McCOY M. GIBSON JR. C. MARSHALL DANN Attesting Officer Commissioner of- Patents F ORM Po-mso (10-69) USCOMM'DC 60376-P69 i I.I.S. GOVERNMENT PRINTING OFFICE I989 0-366-33L 

